1,5-diphenyl derivative of 1H-1,2,4-triazole-3-carboxamide and herbicide containing the same

ABSTRACT

A compound of 1,5-disubstituted .Iadd.-1H-.Iaddend.1,2,4-triazole-3-carboxamide represented by the general formula; ##STR1## wherein R 1  is alkyl of one to three carbon atoms, chloro, fluoro, iodo, trifluoromethyl or nitro, R 2  is hydrogen, methyl or chloro, R 3  is hydrogen or methyl is provided in the invention, which shows an excellent herbicidal activity.

This invention relates to a derivative of 1,2,4-triazole, a process for preparing thereof and a herbicide containing the derivative as an active ingredient.

Certain compounds of 1,2,4-triazole derivative are known to the person skilled in the art as disclosed in for example, J. Amer. Chem. Soc., 79, 1955-1956 (1957), Tetrahedron, 31, 25-29 (1975) and J. Chem. Soc., 575-583 (1962), however in these references there are disclosed no physiological activities, in particular, herbicidal property of the compounds.

It is an object of the invention to provide a compound of 1-substituted phenyl-.[.b.].5-phenyl-.Iadd.1H-.Iaddend.1,2,4-triazole-3-carboxamide. A further object of the invention is to provide a process for preparing the compound. A still further object of the invention is to provide a herbicide containing the compound as an active ingredient.

The compound of the invention is represented by the general formula I: ##STR2## wherein R¹ is alkyl having one to three carbon atoms, chloro, fluoro, iodo, trifluoromethyl or nitro, R² is hydrogen, methyl or chloro, and R³ is hydrogen or methyl, provided that 1-(4-methylphenyl)-5-phenyl-.Iadd.1H-.Iaddend.1,2,4-triazole-3-carboxamide is excluded.

The compound of the invention may be prepared by any appropriate and conventional method, for example, by refluxing 4-substituted .[.phenyl-hydrazono-2-phenyl-oxazoline-5-one.]. .Iadd.phenylhydrazono-2-phenyl-2-oxazolin-5-one .Iaddend.(represented by the general formula II as shown in the reaction scheme below) obtained by the reaction of a corresponding diazonium salt and hippuric acid in a .[.29%.]. methanolic solution of .Iadd.29% .Iaddend.ammonium hydroxide (refer to J. Amer. Chem. Soc., 79, 1956 (1957)), or by contacting a compound of the general formula II with a .[.29%.]. solution of .Iadd.29% .Iaddend.ammonium hydroxide in acetone under reflux followed by adding concentrated hydrochloric acid. These reactions are shown schematically as follows.[.;.]..Iadd.: .Iaddend. ##STR3## wherein R¹, R² and R³ are defined above.

Examples of the compound of the invention are as follows (Table 1), in the Table melting point and the solvent used for recrystallization are also shown. the infrared absorption spectra of each compound are shown in FIGS. 1 to 34 corresponding to the No. of Table 1.

                  TABLE 1                                                          ______________________________________                                         No.              m.p. (°C.)                                                                        solvent                                             ______________________________________                                         .[.1 1-(2-methylphenyl)-                                                                            183-184   C.sub.6 H.sub.6                                      5-phenyl-1,2,4-tri-                                                            azole-3-carboximide.].                                                    1    1-(2-methylphenyl)-                                                            .Iadd.5-phenyl-1H--1,2,4-tri-                                                  azole-3-carboxamide.Iaddend.                                              .[.2 1-(3-methylphenyl)-                                                                            142-143   CH.sub.3 OH--H.sub.2 O                               5-phenyl-1,2,4-tri-                                                            azole-3-carboxamide.].                                                    2    .Iadd.1-(3-methylphenyl)-                                                      5-phenyl-1H--1,2,4-tri-                                                        azole-3-carboxamide.Iaddend.                                              .[.3 1-(2,3-dimethylphen-                                                                           186-188   CHCl.sub.3 --h-C.sub.6 H.sub.14                      y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               3    1-(2,3-dimethylphen-                                                           .Iadd.y1)-5-phenyl-1H--1,2,4-                                                  triazole-3-car-                                                                boxamide.Iaddend.                                                         .[.4 1-(2,4-dimethylphen-                                                                           197-199   CH.sub.3 OH                                          y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               4    .Iadd.1-(2,4-dimethylphen-                                                     y1)-5-phenyl-1H--1,2,4-                                                        triazole-3-car-                                                                boxamide.Iaddend.                                                         .[.5 1-(2,5-dimethylphen-                                                                           171-173   CH.sub.3 OH--H.sub.2 O                               y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               5    .Iadd.1-(2,5-dimethylphen-                                                     y1)-5-phenyl-1H--1,2,4-                                                        triazole-3-car-                                                                boxamide.Iaddend.                                                         .[.6 1-(2,6-dimethylphen-                                                                           185.5-187 CH.sub.3 OH--H.sub.2 O                               y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               6    .Iadd.1-(2,6-dimethylphen-                                                     y1)-5-phenyl-1H--1,2,4-                                                        triazole-3-car-                                                                boxamide.Iaddend.                                                         .[.7 1-(3,4-dimethylphen-                                                                           169-170   CH.sub.3 CH.sub.2 OH--H.sub.2 O                      y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               7    .Iadd.1-(3,4-dimethylphen-                                                     y1-5-phenyl-1H--1,2,4-                                                         triazole-3-car-                                                                boxamide.Iaddend.                                                         .[.8 1-(3,5-dimethylphen-                                                                           166-167.5 CHCl.sub.3 --n-C.sub.6 H.sub.14                      y1)-5-phenyl-1,2,4-                                                            triazole-3-car-                                                                boxamide.].                                                               8    1-(3,5-dimethylphen-                                                                           166-167.5 CHCl.sub.3 --n-C.sub.6 H.sub.14                      y1)-5-phenyl-1H--1,2,4-                                                        .Iadd.triazole-3-car-                                                          boxamide.Iaddend.                                                         .[.9 1-(2,3,4-trimethyl-                                                                            219-221   CH.sub.3 OH--H.sub.2 O                               phenyl)-5-phenyl-1,                                                            2,4-triazole-3-car-                                                            boxamide.].                                                               9    .Iadd.1-(2,3,4-trimethyl-                                                      phenyl)-5-phenyl-1H--1,                                                        2,4-triazole-3-car-                                                            boxamide.Iaddend.                                                         .[.10                                                                               1-(2,4,5-trimethyl-                                                                            202-203.5 CH.sub.3 OH                                          phenyl)-5-phenyl-1,                                                            2,4-triazole-3-car-                                                            boxamide.].                                                               10   .Iadd.1-(2,4,5-trimethyl-                                                      phenyl)-5-phenyl-1H--1,                                                        2,4-triazole-3-car-                                                            boxamide.Iaddend.                                                         .[.11                                                                               1-(3-ethylphenyl)-5-                                                                           176.5-177 CH.sub.3 CH.sub.2 OH--H.sub.2 O                      phenyl-1,2,4-tria-                                                             zole-3-carboxamide.].                                                     11   .Iadd.1-(3-ethylphenyl)-5-                                                     phenyl-1H--1,2,4-tria-                                                         zole-3-carboxamide.Iaddend.                                               .[.12                                                                               1-(4-ethylphenyl)-5-                                                                           199-201   CHCl.sub.3 --n-C.sub.6 H.sub.14                      phenyl-1,2,4-tria-                                                             zole-3-carboxamide.].                                                     12   1-(4-ethylphenyl)-5-                                                           .Iadd.phenyl-1H--1,2,4-tria-                                                   zole-3-carboxamide.Iaddend.                                               .[.13                                                                               1-(3-n-propylphen-                                                                             120-121   CH.sub.3 OH--H.sub.2 O                               y1)-5-phenyl-1,2,4-                                                            triazole-3-carbox-                                                             amide.].                                                                  13   .Iadd.1-(3-n-propylphen-                                                       y1)-5-phenyl-1H--1,2,4-                                                        triazole-3-carbox-                                                             amide.Iaddend.                                                            .[.14                                                                               1-(4-n-propylphen-                                                                             184-186.5 (CH.sub.3).sub.2 CO--n-C.sub.6 H.sub.14              y1)-5-phenyl-1,2,4-                                                            triazole-3-carbox-                                                             amide.].                                                                  14   1-(4-n-propylphen-                                                             .Iadd.y1)-5-phenyl-1H--1,2,4-                                                  triazole-3-carbox-                                                             amide.Iaddend.                                                            .[.15                                                                               1-(4-i-propylphen-                                                                             206-208   CHCl.sub.3 --n-C.sub.6 H.sub.14                      y1)-5-phenyl-1,2,4-                                                            triazole-3-carbox-                                                             amide.].                                                                  15   1-(4-i-propylphen-                                                             .Iadd.y1)-5-phenyl-1H--1,2,4-                                                  triazole-3-carbox-                                                             amide.Iaddend.                                                            .[.16                                                                               1-(2-methyl-3-chlo-                                                                            198-200   CH.sub.3 CH.sub.2 OH                                 rophenyl-5-phenyl-                                                             1,2,4-triazole-3-car-                                                          boxamide.].                                                               16   .Iadd.1-(3-chloro-2-methyl-                                                    phenyl)-5-phenyl-                                                              1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[. 17                                                                              1-(2-chloro-3-meth-                                                                            170-171   CH.sub.3 CH.sub.2 OH--H.sub.2 O                      ylphenyl)-5-phenyl-                                                            1,2,4-triazole-3-car-                                                          boxamide.].                                                               17   .Iadd.1-(2-chloro-3-meth-                                                      ylphenyl)-5-phenyl-                                                            1H--1,2,4-triazole-3-car                                                       boxamide.Iaddend.                                                         .[.18                                                                               1-(2-methyl-4-chlo-                                                                            197-199   CH.sub.3 OH--H.sub.2 O                               rophenyl-5-phenyl-                                                             1,2,4-triazole-3-car-                                                          boxamide.].                                                               18   .Iadd.1-(4-chloro-2-meth-                                                      ylphenyl)-5-phenyl-                                                            1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[.19                                                                               1-(2-chloro-4-meth-                                                                            194-195.5 CHCl.sub.3 --n-C.sub.6 H.sub.14                      ylphenyl-5-phenyl-                                                             1,2,4-triazole-3-car-                                                          boxamide.].                                                               19   1-(2-chloro-4-meth-                                                            .Iadd.ylphenyl)-5-phenyl-                                                      1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[.20                                                                               1-(3-methyl-4-chlo-                                                                            169-171   CHCl.sub.3 --n-C.sub.6 H.sub.14                      ylphenyl)-5-phenyl-                                                            1,2,4-triazole-3-car-                                                          boxamide.].                                                               20   1-(4-chloro-3-meth-                                                            .Iadd.ylphenyl)-5-phenyl-                                                      1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[.21                                                                               1-(3-chloro-4-meth-                                                                            151-153   CHCl.sub.3 --n-C.sub.6 H.sub.14                      ylphenyl)-5-phenyl-                                                            1,2,4-triazole-3-car-                                                          boxamide.].                                                               21   1-(3-chloro-4-meth-                                                            .Iadd.ylphenyl)-5-phenyl-                                                      1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[.22                                                                               1-(3-methyl-4-fluo-                                                                            123-126   CH.sub.3 CH.sub.2 OH--H.sub.2 O                      rophenyl)-5-phenyl-                                                            1,2,4-triazole-3-car-                                                          boxamide.].                                                               22   .Iadd.1-(4-fluoro-3-meth-                                                      ylphenyl)-5-phenyl-                                                            1H--1,2,4-triazole-3-car                                                       boxamide.Iaddend.                                                         .[.23                                                                               1-(3-methyl-5-chlo-                                                                            163.5-165.5                                                                              CHCl.sub.3 --n-C.sub.6 H.sub.14                      rophenyl)-5-phenyl-                                                            1,2,4-triazole-3-car-                                                          boxamide.].                                                               23   1-(5-chloro-3-meth-                                                            .Iadd.ylphenyl)-5-phenyl-                                                      1H--1,2,4-triazole-3-car-                                                      boxamide.Iaddend.                                                         .[.24                                                                               1-(2-chlorophenyl)-                                                                            171-171.5 CHCl.sub.3 --n-C.sub.6 H.sub.14                      5-phenyl-1,2,4-tri-                                                            azole-3-carboxamide.].                                                    24   1-(2-chlorophenyl)-                                                            .Iadd.5-phenyl-1H--1,2,4-tri-                                                  azole-3-carboxamide.Iaddend.                                              .[.25                                                                               1-(3-chlorophenyl)-                                                                            179-180   C.sub.6 H.sub.6                                      5-phenyl-1,2,4-tri-                                                                            (decom-                                                        azole-3-carboxamide.].                                                                         pose)                                                     25   1-(3-chlorophenyl)-                                                            .Iadd.5-phenyl-1H--1,2,4-tri-                                                  azole-3-carboxamide.Iaddend.                                              .[.26                                                                               1-(4-chlorophenyl)-                                                                            186-188   Ch.sub.3 OH                                          5-phenyl-1,2,4-tri-                                                            azole-3-carboxamide.].                                                    26   .Iadd.1-(4-chlorophenyl)-                                                      5-phenyl-1H--1,2,4-tri-                                                        azole-3-carboxamide.Iaddend.                                              .[.27                                                                               1-(2,3-dichlorophen-                                                                           202-204   Ch.sub.3 OH--H.sub.2 O                               yl)-5-phenyl-1,2,4-                                                            triazole-3-carboxamide.].                                                 27   .Iadd.1-(2,3-dichlorophen-                                                     yl)-5-phenyl-1H--1,2,4-                                                        triazole-3-carboxamide.Iaddend.                                           .[.28                                                                               1-(2,4-dichlorophen-                                                                           211-212   CH.sub.3 OH--H.sub.2 O                               yl(-5-phenyl-1,2,4-                                                            triazole-3-carboxamide.].                                                 28   .Iadd.1-(2,4-dichlorophen-                                                     yl)-5-phenyl-1H--1,2,4-                                                        triazole-3-carboxamide.Iaddend.                                           .[.29                                                                               1-(3,4-dichlorophen-                                                                           180-181   CHCl.sub.3 --n-C.sub.6 H.sub.14                      yl)-5-phenyl-1,2,4-                                                            triazole-3-carboxamide.].                                                 29   1-(3,4-dichlorophen-                                                           .Iadd.yl)-5-phenyl-1H--1,2,4-                                                  triazole-3-carboxamide.Iaddend.                                           .[.30                                                                               1-(3-trifluoromethyl-                                                                          147-149   CHCl.sub.3 --n-C.sub.6 H.sub.14                      4-chlorophenyl)-5-                                                             phenyl-1,2,4-tria-                                                             zole-3-carboxamide.].                                                     30   1-(4-chlorophenyl-                                                             .Iadd.3-trifluoromethyl(-5-                                                    phenyl-1H--1,2,4-tria-                                                         zole-3-carboxamide.Iaddend.                                               .[.31                                                                               1-(3-trifluromethyl-                                                                           195-197   CHCl.sub.3 --n-C.sub.6 H.sub.14                      phenyl)-5-phenyl-1,                                                            2,4-triazole-3-car-                                                            boxamide.].                                                               31   1-(3-trifluoromethyl-                                                          .Iadd.phenyl)-5-phenyl-1H--1,                                                  2,4-triazole-3-car-                                                            boxamide.Iaddend.                                                         .[.32                                                                               1-(4-fluorophenyl)-                                                                            185-187   CHCl.sub.3 --n-C.sub.6 H.sub.14                      5-phenyl-1,2,4-tria-                                                           zole-3-carboxamide.].                                                     32   1-(4-fluorophenyl)-                                                            .Iadd.5-phenyl-1H--1,2,4-tria-                                                 zole-3-carboxamide.Iaddend.                                               .[.33                                                                               1-(4-iodophenyl)-5-                                                                            192-193   CHCl.sub.3 --n-C.sub.6 H.sub.14                      phenyl-1,2,4-tria-                                                             zole-3-carboxamide.].                                                     33   1-(4-iodophenyl)-5-                                                            .Iadd.phenyl-1H--1,2,4-tria-                                                   zole-3-carboxamide.Iaddend.                                               .[.34                                                                               1-(3-nitrophenyl)-5-                                                                           217-219   CH.sub.3 OH                                          phenyl-1,2,4-tria-                                                             zole-3-carboxamide.].                                                     34   .Iadd.1-(3-nitrophenyl)-5-                                                     phenyl-1H--1,2,4-tria-                                                         zole-3-carboxamide                                                        ______________________________________                                         .Iaddend.

It is observed that the compound of the invention shows excellent herbicidal activities to broad-leaved plants and grasses, especially to common purslane (Portulaca oleracea), lambs quarters (Chenopodium album), common chickweed (Stellaria media), Wavy bittercress (Cardamine flexuosa) and smart weed (Polygonum longisetum), in herbicidal tests such as germination, soil treatment, foliage treatment, and the like without phytotoxicity to rice, wheat, corn, cotton, and the like as shown in Examples hereinafter.

Therefore, the compound of the invention may be employed for an active ingredient of a herbicide and may be applied to a farm such as a paddy and upland field and a fruit field or .[.a fluoriculture.]. .Iadd.in horticulture.Iaddend..

The compound of the invention may be singly applied or may be applied in the form of a composition diluted to a suitable concentration, for example 30 to 80 p.p.m. by weight, with a diluent used for the conventional herbicides by any appropriate procedure such as spraying onto an object. If necessary, a herbicidal composition of the invention may contain an adjuvant such as a spreader, a wettable agent and a fixing agent. Furthermore, the herbicidal composition may be combined or may be admixed with other physiologically active agent such as a fungicide, an insecticide, a herbicide and a plant growth regulator or a fertilizer, since the compound of the invention is not decomposed or denatured per se and does not decompose or denature other active agents.

An amount of the composition or compound of the invention applied may be varied in the wide range as the conventional herbicide, for example 100 to 300 g of the active ingredient (the compound of the invention) may be applied per 10 are of the field to be treated.

The invention will be further illustrated while referring to the non-limiting examples hereinafter described. From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.

PREPARATION 1 1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide (Compound No. 2 of Table 1)

Three grams (0.01 mole) of .[.4-(3-methylphenylhydrazono)-2-phenyl-oxazoline-5-one.]. .Iadd.4-(3-methylphenylhydrazono)-2-phenyl-2-oxazolin-5-one .Iaddend.(R¹ =3--CH₃, R² =R³ =H in the formula II) was suspended in 93 ml of methanol. To the resulting suspension, 66.2 ml of 29% solution of ammonium hydroxide (0.549 mole) was added and refluxed for 5 minutes. Methanol and ammonia were then distilled off under a reduced pressure, and the resulting crystals were filtered out and washed with water. The crystals were recrystallized from a mixed solvent of 5.8 ml of methanol and 4.5 ml of water to obtain 1.8 g of almost colorless crystal, m.p. 142°-143° C., with a yield of 63% I.R. (KBr, cm⁻¹, refer to FIG. 2); 3500-3240 (broad and strong), 1700, 1670, 1610, 1458, 1400, 1302, 789 and 700.

I.R. (liquid membrane, CHCl₃ solution); .[.3500 (ν_(NH2)).]. .Iadd.(ν_(NH2))3500 .Iaddend.and 3400.

NMR (solvent; d₆ -DMSO, δ, p.p.m.); 2.32 (3H, s, ##STR4## 7.03-7.65 (9H, m, aromatic proton), 7.73, 7.96 (2H, s, --CONH₂), wherein s and m denote singlet and multiplet, respectively.

PREPARATION 2 1-(3,4-dimethylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide (Compound No. 7 of Table 1)

Three grams (0.01 mole) of .[.4-(3,4-dimethylphenylhydrazono)-2-phenyl-oxazoline-5-one.]. .Iadd.4-(3,4-dimethylphenylhydrazono)-2-phenyl-2-oxazolin-5-one .Iaddend.(R¹ =3--CH₃, R² =4--CH₃ and R³ =H in the formula II) was suspended in 16 ml of acetone. To the resulting suspension, 1.57 ml of 29% solution of NH₄ OH (0.013 mole) was added dropwise at room temperature. After refluxing for 25 minutes, heating was stopped and 1.57 ml of concentrated hydrochloric acid was added dropwise. The resulting mixture was again refluxed for 5 minutes. 42 ml of water was then added to the reaction mixture, and obtained crystal was filtered out, washed with acetone containing water and dried. The thus treated crystal was recrystallized from a mixture of 8.8 ml of ethanol and 3 ml of water to obtain 2.25 g of almost colorless crystal, m.p. 169°-170° C., with a yield of 76.9%.

I.R. (KBr, cm⁻¹, refer to FIG. 7); 3500, 3360, 3240, 1699 and 1670.

NMR (solvent; d₆ -DMSO, δ, p.p.m.); 2.22 (3H, s. ##STR5## 7.02-7.74 (8H, m, aromatic proton), 7.85, 8.05 (2H, s, --CONH₂).

PREPARATION 3

.[.1-(2-methyl-3-chlorophenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide.]. .Iadd.1-(3-chloro-2-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide .Iaddend.(Compound No. 16 of Table 1)

6.2 g (0.019 mole) of .[.4-(2-methyl-3-chlorophenylhydrazono)-2-phenyl-oxazoline-5-one.]. .Iadd.4-(3-chloro-2-methylphenylhydrazono)-2-phenyl-2-oxazolin-5-one .Iaddend.(R¹ =2--CH₃, R² =3--Cl and R³ =H in the formula II) was added to 60 ml of acetone with stirring. To the resulting mixture, 3 ml of 29% solution of NH₄ OH (0.024 mole) was added dropwise at room temperature. Then the mixture was refluxed for 25 minutes and heating was stopped. After 3 ml of concentrated hydrochloric acid was added dropwise, and then the mixture was refluxed again for 5 minutes. The obtained reaction mixture was filtred while hot, and 80 ml of water was added to the filtrate. The obtained mixture was allowed to stand for cooling to obtain a product. The product was filtered out, washed with acetone containing water and dried. The crystal was recrystallized from 60 ml of ethanol to obtain 4.8 g of almost colorless crystal, m.p. 198°-200° C., with a yield of 78.2%.

I.R. (KBr, cm⁻¹, refer to FIG. 16); 1680, 1470, 1300 and 780.

NMR (solvent; d₆ -DMSO, δ, p.p.m.); 1.98 (3H, s, ##STR6## 7.35-7.8 (8H, m, aromatic proton), 7.85, 8.1 (2H, s, --CONH₂).

PREPARATION 4

.[.1-(3-methyl-4-fluorophenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide.]. .Iadd.1-(4-fluoro-3-methylphenyl)-5-phenyl-1H 1,2,4-triazole-3-carboxamide .Iaddend.(Compound No. 22 of Table 1)

3.0 g (0.01 mole) of .[.4-(3-methyl-4-fluorophenylhydrazono)-2-phenyl-oxazoline-5-one.]. .Iadd.4-(4-fluoro-3-methylphenylhydrazono)-2-phenyl-2-oxazolin-5-one .Iaddend.(R¹ =3--CH₃, R² =4--F and R³ =H in the formula II) was suspended in 16 ml of acetone. To the suspension, 1.57 ml of 29% solution of NH₄ OH (0.013 mole) was added dropwise at room temperature. After refluxing the reaction mixture for 25 minutes, heating was stopped and 1.57 ml of concentrated hydrochloric acid was added dropwise. After the addition was over, the reaction mixture was refluxed again for 5 minutes. Then 40 ml of water was added to the reaction mixture, and the resulting crystal was filtered out, washed with acetone containing water and dried. The obtained crystal was recrystallized from a mixture of 20 ml of ethanol and 5 ml of water to obtain 1.7 g of almost colorless crystal, m.p. 123°-126° C., with a yield of 55.2%.

I.R. (KBr, cm⁻¹, refer to FIG. 22); 1690, 1660, 1490, 1400, 1300, 1290, 1230, 1190, 1000, 740 and 690.

NMR (solvent; d₆ -DMSO, δ, p.p.m.); 2.37 (3H, d, J=2Hz, ##STR7## 7.35-7.8 (8H, m, aromatic proton), 7.85 and 8.10 (2H, s, --CONH₂), wherein d and J denotes doublet and coupling constant, respectively, and s and m are defined above.

    ______________________________________                                         FORMULATION 1                                                                  Wettable powder                                                                Component       Parts by weight                                                ______________________________________                                         Compound No. 2  50                                                             ligninsulfonate 5                                                              alkylsulfonate  3                                                              diatomaceous earth                                                                             42                                                             ______________________________________                                    

These components were mixed and pulverized to obtain a wettable powder which may be applied after diluting with water.

    ______________________________________                                         FORMULATION 2                                                                  Emulsion                                                                       Component           Parts by weight                                            ______________________________________                                         Compound No. 7      25                                                         xylene              65                                                         polyoxyethylene alkyl aryl ether                                                                   10                                                         ______________________________________                                    

These components were uniformly mixed to obtain an emulsifiable formulation which may be applied after diluting with water.

    ______________________________________                                         FORMULATION 3                                                                  Granulation                                                                    Component       Parts by weight                                                ______________________________________                                         Compound No. 16 8                                                              bentonite       40                                                             clay            45                                                             ligninsulfonate 7                                                              ______________________________________                                    

These components were uniformly mixed, kneaded with water, granulated from an extrusion granulator and dried to obtain a granule.

The effectiveness of the compound of the invention as a herbicide is illustrated while referring to the examples as follows.

EXAMPLE 1 Germination

In each glass dish of 9 cm in diameter, 2 sheets of filter paper were placed in layers. After pouring 5 ml of an aqueous suspension of each compound of the invention (concentration of the active ingredient being 25 or 50 ppm) on the filter paper, 15 seeds of each test plant shown in Table 2 were placed on the filter paper. The thus prepared dishes were placed in a room at a controlled temperature of 25° C. under light condition. After 4 days of placing, the state of germination of the seeds was investigated, and after leaving the dishes for further six days as they were, the state of growth-inhibition of the germinated weeds and the crop plants was observed by naked eyes and judged according to the standard scale from 0 (corresponding to no inhibition) to 5 (no germination or withered after germination). The results of observation were shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     Concentra-                                                                            Compound No.                                                            tion   1   2   3   4   5   6   7   8   9   10  11  12  13  14                  (ppm)  25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                __________________________________________________________________________     Oryza sativa                                                                          1 3 4 5 1 4 2 2 0 1 0 0 3 5 0 0 1 1       1                                                                              1                                                                              2                                                                              4 0 1 2 2    0                                                                         1                     Echinochloa                                                                           2 3 5 5 3 5 5 5 1 2 0 0 4 5 0 0 2 3       2                                                                              2                                                                              3                                                                              4 0 1 2 2    0                                                                         0                     crus-galli                                                                     var.                                                                           frumentacea                                                                    Cyperus iria                                                                          0 1 4 5 3 5 3 5 1 2 2 4 5 5 1 3 2 2       1                                                                              1                                                                              5                                                                              5 0 1 1 1    0                                                                         0                     Portulaca                                                                             5 5 5 5 5 5 5 5 5 5 2 3 5 5 5 5 2 5       5                                                                              5                                                                              5                                                                              5 2 5 5 5    5                                                                         5                     oleracea                                                                       Chenopodium                                                                           5 5 5 5 5 5 5 5 5 5 2 2 5 5 5 5 5 5       5                                                                              5                                                                              5                                                                              5 3 5 5 5    5                                                                         5                     album                                                                          __________________________________________________________________________     Concentra-                                                                            Compound No.                                                            tion   15  16  17  18  19  20  21  22  23  24  25  26  27  28                  (ppm)  25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                __________________________________________________________________________     Oryza sativa                                                                          1 1 5 5 4 5 0 0 0 0 4 4 4 4 4 4 1 3       3                                                                              3                                                                              3                                                                              4 0 4 0 3    1                                                                         0                     Echinochloa                                                                           1 1 5 5 5 5 1 4 0 2 4 4 3 4 4 5 0 1       0                                                                              2                                                                              2                                                                              2 1 4 1 4    1                                                                         1                     crus-galli                                                                     var.                                                                           frumentacea                                                                    Cyperus iria                                                                          0 0 4 5 4 5 0 2 1 3 5 5 3 4 5 5 0 2       1                                                                              1                                                                              1                                                                              3 0 2 1 2    0                                                                         1                     Portulaca                                                                             0 1 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3 5       5                                                                              5                                                                              5                                                                              5 5 5 5 5    5                                                                         5                     oleracea                                                                       Chenopodium                                                                           1 3 5 5 5 5 5 5 3 5 5 5 5 5 5 5 5 5       3                                                                              5                                                                              5                                                                              5 5 5 5 5    2                                                                         2                     album                                                                          __________________________________________________________________________                                Concentra-                                                                            Compound No.                                                            tion   29  30  31  32  33  34  Control                                         (ppm)  25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                               50                                                                               25                                                                                50                                                                              --                   __________________________________________________________________________                                Oryza sativa                                                                          0 2 1 1 0 2 0 0 0 1 0 1 0                                               Echinochloa                                                                           0 1 0 0 1 2 2 2 0 0 0 0 0                                               crus-galli var.                                                                frumentacea                                                                    Cyperus iria                                                                          1 2 0 0 0 1 0 1 0 1 0 0 0                                               Portulaca                                                                             5 5 2 2 5 5 3 5 1 2 3 5 0                                               oleracea                                                                       Chenopodium                                                                           5 5 2 3 5 5 5 5 3 5 2 5 0                                               album                                               __________________________________________________________________________

EXAMPLE 2 Soil treatment before germination

Into a planter of 650 mm in length, 210 mm in width and 200 mm in height, soil taken from a farm land was placed, and a predetermined amount of seeds of each one of weeds and crop plants shown in Table 3 was sown. After one day of covering the sown seeds thinly with light soil, 30 ml of an aqueous suspension of each compound of the invention was sprayed on the whole surface of the soil in the planter (corresponding to 300 g of the compound to be sprayed on 10 are of the soil surface). After 35 days of the spraying, the inhibiting effect of each compound on the growth of the weed and the phytotoxicity of each compound on the crop plant were observed by naked eyes, and the result of observation was converted into one of the indices shown below by the following standards, and is shown in Table 3.

    ______________________________________                                         Standards:                                                                     ______________________________________                                         (1) Effect of inhibiting the growth of weeds:                                  Index          Result of observation                                           ______________________________________                                         0:             no inhibition                                                   1:             extent of inhibition 20%                                        2:             extent of inhibition 40%                                        3:             extent of inhibition 60%                                        4:             extent of inhibition 80%                                        5:             complete inhibition                                             ______________________________________                                         (2) Phytotoxicity to crop plants:                                              Index          Result of observation                                           ______________________________________                                         0:             no harm                                                         1:             very slight harm                                                2:             slight harm                                                     3:             moderate harm                                                   4:             severe harm                                                     5:             whitered or not germinated                                      ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     Compound No.                                                                              1 2 3 4 5 6 7 8 9 10                                                                               11                                                                               12                                                                               13                                                                               14                                                                               15                                                                               16                                                                               17                                                                               18                                                                               19                                                                               20                                                                               21                                                                               22                                                                               23                                                                               24                                                                               25                                                                               26                __________________________________________________________________________     Oryza sativa                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0       0                                                                              0                                                                              0                                                                              0 0 0 0 0                 Triticum sativum                                                                          0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0       0                                                                              2                                                                              2                                                                              1 0 0 0 0                 Zea mays   0 0 0 0 0 0 2 0 0 0 1 0 0 0 0 1 0 0       0                                                                              1                                                                              0                                                                              0 0 0 0 0                 Glycine soja                                                                              3 5 3 2 2 1 5 2 0 1 3 1 3 2 0 4 4 3       3                                                                              4                                                                              5                                                                              3 1 3 3 3                 Gossypium arboreum                                                                        0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0       0                                                                              0                                                                              0                                                                              0 0 0 0 0                 Digitaria sanguinalis                                                                     1 4 3 3 2 0 4 0 0 0 3 2 1 1 0 4 3 3       3                                                                              4                                                                              4                                                                              4 0 3 2 2                 Poa annua  1 5 5 4 5 0 5 0 0 0 5 3 1 0 0 5 5 4       3                                                                              5                                                                              5                                                                              4 2 0 3 3                 Stellaria media                                                                           4 5 5 5 5 1 5 5 1 1 5 5 2 1 1 5 5 5       5                                                                              5                                                                              5                                                                              5 2 4 5 4                 Cardamine flexuosa                                                                        4 5 5 5 5 2 5 5 1 1 5 5 3 2 1 5 5 5       5                                                                              5                                                                              5                                                                              5 1 0 5 5                 Portulaca oleracea                                                                        4 5 5 5 5 1 5 4 1 1 5 5 2 1 1 5 5 5       5                                                                              5                                                                              5                                                                              5 2 3 4 4                 Chenopodium album                                                                         3 5 5 5 5 1 5 5 0 0 4 4 2 0 0 5 5 4       4                                                                              5                                                                              5                                                                              5 1 5 4 4                 Polygonum longisetum                                                                      4 5 4 4 4 0 5 5 0 0 4 3 1 0 0 5 5 4       3                                                                              5                                                                              5                                                                              4 1 5 4 4                 __________________________________________________________________________                                    Compound No.                                                                              27                                                                               28                                                                               29                                                                               30                                                                               31                                                                               32                                                                               33                                                                               34                                                                               Control              __________________________________________________________________________                                    Oryza sativa                                                                              0 0 0 0 0 0 0 0 0                                                   Triticum sativum                                                                          0 0 0 0 1 2 0 0 0                                                   Zea mays   0 0 0 1 0 1 0 0 0                                                   Glycine soja                                                                              3 2 4 3 2 3 0 1 0                                                   Gossypium arboreum                                                                        0 0 0 0 0 0 0 0 0                                                   Digitaria sanguinalis                                                                     2 3 3 4 3 3 2 0 0                                                   Poa annua  2 4 5 4 4 1 0 0 0                                                   Stellaria media                                                                           4 5 5 5 5 5 0 1 0                                                   Cardamine flexuosa                                                                        4 5 5 5 5 5 0 0 0                                                   Portulaca oleracea                                                                        4 5 5 5 5 5 1 1 0                                                   Chenopodium album                                                                         3 4 5 5 5 5 0 0 0                                                   Polygonum longisetum                                                                      3 4 5 5 4 5 1 0 0                    __________________________________________________________________________

EXAMPLE 3 Soil treatment after germination

Into a planter of the same size as that used in Example 2, soil taken from a farm land was placed, and a predetermined amount of seeds of each one of weeds and crop plants shown in Table .[.3.]. .Iadd.4 .Iaddend.was sown and the planter was left to stand for a period after which the germinated plants reached to their 2 to 3-true leaf stage. Then, aqueous suspension of each compound of the invention (corresponding to 300 g/10 are of the surface area of the soil in the planter) was sprayed uniformly onto the surface of the soil in the planter including the young plants therein. After 35 days of the spraying, the state of growth-inhibition of the weeds and the extent of phytotoxicity to the crop plants were observed by naked eyes. The result of observation was expressed by the following indices according to the standards shown in Example 2, and shown in Table 4.

                                      TABLE 4                                      __________________________________________________________________________     Compound No.                                                                              1 2 3 4 5 6 7 8 9 10                                                                               11                                                                               12                                                                               13                                                                               14                                                                               15                                                                               16                                                                               17                                                                               18                                                                               19                                                                               20                                                                               21                                                                               22                                                                               23                                                                               24                                                                               25                                                                               26                __________________________________________________________________________     Oryza sativa                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0       0                                                                              0                                                                              0                                                                              0 0 0 0 0                 Triticum sativum                                                                          0 0 0 0 1 0 2 0 0 0 1 0 0 0 0 1 0 0       0                                                                              2                                                                              0                                                                              0 0 0 2 0                 Zea mays   0 1 1 0 1 0 0 1 0 0 1 1 0 0 0 1 1 1       0                                                                              1                                                                              1                                                                              1 0 0 1 0                 Glycine soja                                                                              4 5 4 3 3 2 5 3 1 2 4 4 1 1 1 5 4 3       4                                                                              3                                                                              5                                                                              5 2 2 4 2                 Gossypium arboreum                                                                        0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0       0                                                                              0                                                                              0                                                                              0 0 0 0 0                 Digitaria sanguinalis                                                                     0 2 3 2 1 0 5 4 0 0 2 1 0 0 1 3 3 2       2                                                                              3                                                                              2                                                                              3 0 4 0 1                 Poa annua  0 4 3 3 4 1 5 0 0 1 3 1 0 2 1 5 3 2       3                                                                              4                                                                              2                                                                              2 1 0 1 3                 Stellaria media                                                                           3 5 4 4 5 2 5 3 2 2 4 2 2 2 2 5 5 5       5                                                                              5                                                                              5                                                                              5 3 3 4 3                 Cardamine flexuosa                                                                        3 5 5 4 5 2 5 3 2 2 4 2 2 2 2 5 5 5       5                                                                              5                                                                              5                                                                              5 3 3 4 3                 Portulaca oleracea                                                                        4 5 5 4 4 3 5 1 1 2 4 2 1 1 2 5 5 3       4                                                                              5                                                                              5                                                                              5 2 0 3 2                 Chenopodium album                                                                         3 5 5 5 5 2 5 1 2 2 4 3 1 0 0 5 5 4       4                                                                              5                                                                              5                                                                              5 2 0 3 4                 Polygonum longisetum                                                                      3 5 5 4 4 2 5 2 2 1 3 3 1 0 0 5 5 4       4                                                                              5                                                                              5                                                                              5 3 2 3 3                 __________________________________________________________________________                                    Compound No.                                                                              27                                                                               28                                                                               29                                                                               30                                                                               31                                                                               32                                                                               33                                                                               34                                                                               Control              __________________________________________________________________________                                    Oryza sativa                                                                              0 0 0 0 0 0 0 0 0                                                   Triticum sativum                                                                          0 0 0 2 1 0 0 0 0                                                   Zea mays   1 0 0 1 1 0 1 0 0                                                   Glycine soja                                                                              3 3 3 5 5 4 1 0 0                                                   Gossypium arboreum                                                                        0 0 0 0 0 0 0 0 0                                                   Digitaria sanguinalis                                                                     1 2 3 4 2 4 0 0 0                                                   Poa annua  2 3 2 3 2 0 0 0 0                                                   Stellaria media                                                                           5 5 5 5 5 5 1 2 0                                                   Cardamine flexuosa                                                                        5 5 5 5 5 5 0 1 0                                                   Portulaca oleracea                                                                        4 3 5 5 4 5 0 0 0                                                   Chenopodium album                                                                         3 4 5 5 4 0 0 0 0                                                   Polygonum longisetum                                                                      4 3 5 4 4 1 0 0 0                    __________________________________________________________________________

EXAMPLE 4 Foilage treatment

To the leaves and stems of 4 species of weeds grown in an unglazed porcelain pot containing soil from a farm land at their 2 to 3 leaf-stage, an aqueous suspension of each compound of the invention at a concentration of 1000 ppm was sprayed and the weeds were cultured, and after 14 days of the spraying, the herbicidal effect on the weeds was observed by naked eyes, and the results are expressed by one of the indices used in Example 2, and shown in Table 5.

                  TABLE 5                                                          ______________________________________                                         Compound No.                                                                               1      2     3   4   5   6   7   8   9   10                        ______________________________________                                         Poa annua   0      3     0   0   0   0   0   0   0   0                         Stellaria media                                                                            5      5     3   2   3   0   3   3   0   0                         Portulaca oleracea                                                                         5      5     3   2   5   2   3   5   0   0                         Cardamine flexuosa                                                                         5      5     5   4   4   0   4   3   0   0                         ______________________________________                                         Compound No.                                                                               11     12    13  14  15  16  17  18  19  20                        ______________________________________                                         Poe annua   0      0     0   0   0   2   3   0   0   0                         Stellaria media                                                                            2      0     5   0   0   4   5   4   3   3                         Portulaca oleracea                                                                         3      4     5   1   3   5   2   4   4   4                         Cardamine flexuosa                                                                         4      1     5   0   0   5   5   5   4   4                         ______________________________________                                         Compound No.                                                                               21     22    23  24  25  26  27  28  29  30                        ______________________________________                                         Poa annua   0      0     0   0   0   0   0   0   0   1                         Stellaria media                                                                            5      5     1   1   2   3   4   4   4   5                         Portulaca oleracea                                                                         5      5     2   2   3   3   3   3   3   5                         Cardamine flexuosa                                                                         5      5     1   3   5   4   3   4   4   4                         ______________________________________                                         Compound No.                                                                               31       32    33    34  Control                                   ______________________________________                                         Poa annua   0        0     0     0   0                                         Stellaria media                                                                            3        3     0     3   0                                         Portulaca oleracea                                                                         4        3     0     0   0                                         Cardamine flexuosa                                                                         4        4     0     4   0                                         ______________________________________                                     

What is claimed is:
 1. A .[.1,5-disubstituted-1,2,4-triazole-3-carboxamide.]. .Iadd.1,5-disubstituted-1H-1,2,4-triazole-3-carboxamide .Iaddend.having the formula: ##STR8## wherein R¹ is an atom of fluorine or chlorine, a methyl group or a trifluoromethyl group; R² is an atom of chlorine or a methyl group; and R³ is an atom of hydrogen or a methyl group.
 2. .[.1-(3,4-dimethylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide.]. .Iadd.1-(3,4-dimethylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide.Iaddend.. .[.3. 1-(2-methyl-3-chlorophenyl)-5-phenyl-1,2,4-triazole-3-carboxamide..].
 4. 1-(2-chloro-3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide..]. .[.5. 1-(3-methyl-4-chlorophenyl)-5-phenyl-1,2,4,-triazole-3-carboxamide..].
 6. .[.1-(3-chloro-4-methylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide.]. .Iadd.1-(3-chloro-4-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide.Iaddend.. .[.7. 1-(3-methyl-4-fluorophenyl)-5-phenyl-1,2,4-triazole-3-carboxamide..].
 8. A herbicide composition comprising as an active ingredient a herbicidally effective amount of a 1.5-disubstituted 1,2,4-triazole-3-carboxamide represented by the formula: ##STR9## wherein R¹ is an alkyl group having 1 to 3 carbon atoms, a trifluoromethyl group, a chlorine atom, fluorine atom, an iodine atom or a nitro group, R² is .Iadd.a hydrogen atom, .Iaddend.a methyl group or a chlorine atom and R³ is a methyl group or a hydrogen atom, provided that 1-(4-methylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide is excluded, together with a herbicidally acceptable carrier or a diluent. .[.9. The herbicide composition according to claim 8 in which the 1,5-disubstituted 1,2,4-triazole-3-carboxamide is 1-(3-methylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide..].
 10. A method for controlling noxious weeds, which comprises applying to said noxious weeds or to land a herbicide composition comprising as an active ingredient a herbicidally effective amount of a 1,5-disubstituted 1,2,4-triazole-3-carboxamide represented by the formula: ##STR10## wherein R¹ is an alkyl group having 1 to 3 carbon atoms, a trifuoromethyl group, a chlorine atom, a fluorine atom, an iodine atom or a nitro group; R² is .Iadd.a hydrogen atom, .Iaddend.a methyl group or a chlorine atom and R³ is a methyl group or a hydrogen atom, provided that 1-(4-methylphenyl)-5-phenyl-1,2,4-triazole-3-carboxamide is excluded, together with a herbicidally acceptable carrier or a diluent. The method according to claim 10 in which said carboxamide is .[.1-(3-methyl-phenyl)-5-phenyl-1,2,4-triazole-3-carboxamide.]..Iadd.1-(3- methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide.Iaddend.. .Iadd.12. 1-(3-chloro-2-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide. .Iaddend. .Iadd.13. 1-(4-chloro-3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide. .Iaddend. .Iadd.14. 1-(4-fluoro-3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide. .Iaddend. .Iadd.15. The herbicide composition according to claim 8 in which the 1,5-disubstituted-1H-1,2,4-triazole-3-carboxamide is 1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide..Iaddend. 